Triazine derivatives



Patented Sept. 15, 1942 2,295,562 ramznvn DERIVATIVES Gaetano F. DAlelio andJames W. Underwood, Pittsfield, Mass, assignors to General Electric Company, a corporation of New York No Drawing. Application June 27, 1 941,

. Serial No. 400,151

12 Claims.

This invention relates to new chemical compounds and more particularly to triazine derivatives. The invention especially is concerned with the production of new and useful s-triaz-inyl carbamyl-alkyl sulfides and s-triazinyl thiocarbamyl-alkyl sulfides (s-triazinyl-thio-acylamides and s-triazinyl-thio-acylthioamides).

The triazine derivatives of this invention may be illustrated graphically by'the following general formula In the-above formula 11. represents an integer and is at least 1 and not more than 3, :1: is an integer and is at least 1 and not more than 2, Y represents a member of the class consisting of oxygen and sulfur, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, numerous examples of which hereafter are given. Since :1: represents an integer which is 1 r 2, it will be seen that the linkage of the I (BEN)- carbamyl-alky1 (or thiocarbamyl-alkyl)- group to amyl, hexyl, etc.), including cycloaliphatic (e. g.,

cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.); aryl (e. g., phenyl, diphenyl, naphthyl, etc.); alkaryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, etc.); aralkyl (e. g., benzyl, phenylethyl, phenylpropyl, etc.); and their homologues, as well as those groups with one or more of their hydrogen atoms substituted by, for example, a halogen.

Specific examples of halogeno-substituted hydrocarbon radicals are chlorphenyl, chlorcyclohexyl, chlormethyl, dichlorphenyl, ethyl chlorphenyl,

'phenyl chlorethy1, bromethyl, bromtolyl, etc.

Preferably R is hydrogen.

Our new triazine derivatives may be used as chemotherapeutic agents and, also, as intermediates in the preparation of other compounds. For example, they may be employedas intermediates in the preparation of derivatives thereof such as imido ether, amidine, acyl, ureido, hydrazino, etc., derivatives of the individual triazinyl carbamyl-alkyl (or thiocarbamyl-alkyl) sulfide. These new organic sufides are especially valuable in the preparation of synthetic resinous compositions. Thus, they may be condensed with, for instance, aldehydes, including polymeric aldehydes and aldehyde-addition products, to yield condensation products of particular utility in the plastics and coating arts. Such condensation products are more fully described and are specifically claimed in our copending application Serial No. 400,148, .flled concurrently herewith and assigned to the same assigne as the present invention. The aldehyde-addition products of our new triazine derivatives also may be compounded with rubber, both natural and synthetic, to modify the properties of the rubber.

Various methods may be employed to produce the chemical compounds of this invention. We prefer to prepare them by effecting reaction between a mercapto symmetrical triazine (s-triazine) and a mono-halogenated alkyl amide or thioamide in the presence of a hydrohalide acceptor. Illustrative examples of mercapto s-triazines that may be used, depending upon the particular s-triazinyl carbamyl-alkyl (or thiocarbamyl-alkyl) sulfide desired, are:

s-tri- Typical examples of mono-halogenated alkyl amides and thioamides that may be employed,

depending upon the particular end-product sought, are:

' Beta-chloro alpha-ethyl propionamide Beta-chloro alpha-ethyl propionthioamide Alpha-bromo alpha-methyl beta-chlorphenyl butyramide Alpha-chloro alpha-ethyl beta-phenyl butyrthioamide N-cyclohexyl pionamide Illustrative examples of hydrohalide acceptors that may be used are the inorganic bases, e. g., the alkalimetal hydroxides (sodium hydroxide, potassium hydroxide, etc.), calcium hydroxide, barium hydroxide, ammonium hydyroxide;.,etc., the carbonates of such bases, and the organic bases, e. g., tertiary amines such, for instance, as trimethyl amine, tributyl amine, dimethyl aniline, pyridine, quinoline, etc., quaternary ammonium bases (e. g.,-tetramethy1 ammonium hydroxide, etc), and the like. Preferably the hydrohalide acceptor is one that will react with the mercapto s-triazine to form a water-soluble salt. Examples of such preferred acceptors are sodium and potassium hydroxides.

The reaction between the mercapto s-triazine and the mono-halogenated alkyl amide or thioamide may be carried out in any suitable manner, but preferably is effected in the presence of a suitable solvent or mixture of solvents. Although various solvents or solvent mixtures may be employed we prefer, for economic reasons and because of their eminent suitability, to use water or a mixture of water and alcohol. The reaction may be carried out under a variety of temperature and pressure conditions, for instance at normal or at elevated temperatures and at atmosmeta-bromo alpha-propyl propheric, sub-atmospheric or super-atmospheric pressures.

The above reaction may be represented by the following general equation:

In the above equation X represents halogen and R, Y, n and a: have the same meanings as given above with reference to the general Formula I for the triazine derivatives of this invention.

Our new chemical compounds also may be prepared by eflecting reaction between a halogenated s-triazine and a mono-mercapto alkyl amide or thioamide in the presence of a hydrohalide acceptor. This reaction may be carried out by any suitable means but preferably is effected in the presence of an anhydrous solvent, e. g., alcohol. The other conditions of reaction may be the same as described above with reference to the firstmentioned method of preparation.

Illustrative examples of halogenated s-triazines which may be used, depending upon the desired end-product, are:

6-chloro 2,4-diamino s-triazine (2-chloro 4,6 diamino s-triazine) 6-i0d0 2,4-diamino s-triazine 4,6-dichloro 2-amino s-triazine 2,4,6-trichloro s-triazine 6-chloro 2,4-di-(methylamino) s-triazine 4-chloro 2-amino 6-ani1ino s-triazine 2-chloro 4-toluido fi-ethylamino s-triazine 4,6-dibromo 2-cyclohexylamino s-triazine 6-iodo 2,4-di-(benzylamino) s-triazine Illustrative examples of mono-mercapto alkyl amides and thioamides that may be used, depending upon the particular product desired, are:

N-methyl mercapto acetamide N-phenyl mercapto acetamide Mercapto acetamide Mercapto acethioamide Alpha-mercapto butyramide Alpha-mercapto butyrthioamide Beta-mercapto alpha-phenyl propionate Beta-mercapto alpha-phenyl propionthioamide Beta-mercapto beta-chlorphenyi propionamide Beta-mercapto beta-phenyl propionthioamide Beta-mercapto alpha-benzyl alpha-methyl butyramide- Beta-mercapto alpha-phenyl alpha-ethyl butyrthioamide Alpha-mercapto beta-tolyl butyramide Alpha-mercapto beta-benzyl butyrthioamide N-butyl alpha-mercapto beta-benzyl butyramide N-cyclohexyl beta-mercapto alpha-phenyl propionthioamide The hydrohalide acceptor may be the same as described above with reference to the first-named method of preparing the compounds of this invention.

The general reaction for this alternative methcd of preparing our new chemical compounds is illustrated by the following equation I n -Qt). +..Hs-(o Bor -Nan meanings as defined hereinbefore with reference to Formula I and Equation II.

In order that those skilled in'the art better may understand how the present invention may be carried into effect, the following specific exand washed well with water.

"amino s-triazinyl di-(carbamyl-methyl sulfide).

amples thereof are given. All parts are by weight.

Example 1 This example illustrates the preparation of 4,6-diamino s-triazinyl-2 carbamyl-methyl sulfide, the formula for which is The above ingredients were dissolved in a solvent mixture comprising 1,000 parts water and 1,000 parts alcohol. The mixture was allowed to react at room temperature with vigorousstirring for 4 hours, followed by heating for 1 hour a on a boiling water bath. After cooling the reaction mix, the precipitated product comprising 4,6-diamino s-triazinyl-Z carbamyl-methyl 8111? fide was filtered oil andwashed well with water. The washed product was dried. The yield was 1'73 parts. No attempt was made to recover more from the mother liquor.

Example 2 This example illustrates the preparation of 4,6-diamino s-triazinyl-2 phenylcarbamyl-methyl sulfide, the formula for which is N me r -s-cu'r-comzclm P 4,6-diamino Z-mercapto s-triazine 143.0 Alpha-chloracetanilide 1.5 Sodium hydroxide (hydrohalide acceptor)- ide The above ingredients were dissolved in a solvent mixture compg 500 5: water and 5 parts alcohol. The mixture was allowed to react at room temperature for 120 hours. followed by heating for 1 hour on a boiling water bath. After cooling the reaction mix, the precipitatw product comprising 4,6-diamino is it 1-2 phenylcarbamyl-methyl sulfide was filtered 0d 7 'fhe atits. ed product was dried. The yield was 17% parts. No attempt was made to recover more from the mother liquor.

As will be readily understood by those 1 in the art, when it is desired to produce compounds containing a single monoo n. grouping and two carbamyl-l de grounings or compounds containing a tri w. mun ing and three carbamyl-alml sulfide gross. thenthe starting reactants and proportions of reactants are chosen so as to yield the w 1 products in accordance with methods such as above given by way of illustration.

From the foregoing description it will be that the present invention provides new and useful s-triazinyl carhannvi-alml sulfides, examples of which are s-triazinyl tri-(carhamyl-methyl sulfide), s-triazinyl tri-(carbamyl-ethyi sulfide) s-triazinyl tri-(thiocarbamyl-methyl sulfide), s-

triazinyl tri-(thiocarbamvl-ethyif sulfide); monothe monoamino (-NHR) s-triazinyl di-(thiocarbamyl-methyl sulfides). the monoamino (-NHR) s-triazinyl di-(carbamyl-ethyl sulfides), the monoamino (-NHR) s-triazinyl di- (thiocarbamyl-ethyl sulfide). the diamino [(-NHRM] s-triazinyl mono-(carbamyl-meth- 7i suliides),the diammo [(-NHR) a] s-triazinyl mono-(thiocarbamyl-methyl sulfides), the diamino [(-NHRJal s-triazinyl mon'o-(carbamylethyl sulfides) and the diamino [(N'HR):] striazinyi mono-(thiocarbamyl-ethyi sulfides). Other and more specific examples of these new compounds are shown below:

Han-0 c-sc nr-c 8 NH:

it t C I 4,6-dinmino s-triaeinyl-2 thiocnrbamyl-methyl sulfide VII HrNO C CHICHI S? -CHr-CKz-C ONE:

s-triasinyl-2,4,6 tri-(beta-carbamyl-ethyl sulfide) HaN(lJ (1-8 -0 m-c-omn VIII sCHr-CONm s-triszinyl-Z,4 di-(carbsmyl-methyl sulfide) Loin-0 sum v striazinyl-Zi di-(thiocarbamyl-mothyl sulfide) xxx x111 4 N Cam,

. (I) mN-c -s-oH,osNE-c.m cumnN-t i o-sn-co nolm N xxn N\ c 5 o CsHs 1113-03, -CB-0.0NHOoHr d-amino 4-snilino striazinyl-Z phenylthiocerbumyl-methyl sulfide o'mphthyhmmo fi f XIV 1 m 0 0' s-cn-ooNn mN-c c-s-crr-osNm I ll lHaCI N N xxm -CH-CONH I'm-can V H 01 s-amino 4 aniline s-triazlnyl 2 thiocarbamyl phenylmethyl sulfide y WM, :ugidcgrbmylmommnflmemyl 6 xv xxrv N .cH,-HN-c CSCH:OH:-CONH:

I I HGSHICHNB c-cm-s-o o-s-cm-c s NHCHiCOHS N I ll NH-c A cm-c SNHCH c m a a I d-methylamino 4-toluido s-triazinyi 2 betiwsrbsmyl-ethyl sulfide k y 6 m (bomyltmmmyl momyl mmdo) XVI 4 xxv 01m N can F mNoc-cn-dn-s-c i -s-cn-cacoNm N N N 3H8 C C 00H:

1 NIP-0.1% L-cn-(En-oomn ti-methylami'no 4-snilino s-trlamumylld phenylthiocarbemyl-methyl 4,6-diamino s-trlazinyl-Z alpha-thiocarbamyl-ethyl sulfide XVIII N OHS-05H} xCkCuHr-HN-(f H-CHzCSNE-CH;

N N N g NIj-CJr-Cflm 4,6-di-toluido s-triazinyl-2 bets-(gammagihenyl methylthioan'bemylpropyl)sulii e CeHuHN(l) G-S-(gH-CHr-CH:

CSNHCiHs E NH-CeHu triasinyi-2 alpba-phenylthiocarbamylp sulfide 4,6-di-(cyclohexylamino) spro yi all s-triazinyl-L, 4, 6 tri-[beta-(alpha-phenyl e arbamyi-butyl) sulfide XXVI N A C H: 0 ONE:

o-amino s-triszinyl flr-thiocarbamyl-methyl i-earbamyl-metbyl .disulflde eneral formula IN v I 1 Y Ma ("3:1 s-(cm).-t"-Nan1 where n is an integer and is at least 1 and not more than 3, a: is an integer and is at least 1 and not more than 2, R is a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals. and Y is a member of the class consisting of oxygen and sulfur. ,4

2. Chemical compounds as in claim 1 wherein R represents hydrogen.

3. Chemical compounds as in claim 1 wherein It represents hydrogen and Y represents oxygen.

4. Chemical compounds as in claim 1 wherein R-represents hydrogen, Y represents oxygen and a: is 1. o

5-. Symmetrical triazinyl-2,4,6 tri-carbamylmethyl sulfide); v

6. A monoamine s-triazinyl di-carbamylmethyl sulfide).

. pounds corresponding to the general formula spouses I. B-amino s-triazinyl-zA di-carbamyl-methyl (l) a mercapto triatine corresponding to the gen sulfide) eral formula a. A iemme s-triazinyl carbamyl-metbyl sule. V

9. 4,6-diamino s-triazinyl-z-carbamyl-methyl I sulfide l0. 'i'he method or preparing chemical com- Y sponding to the general formula 0 sg" Y l 1} s Bor -NEE]- L. .X-(cam-A-nna E J 15 where 1: represents halogen and R, Y, 11 and a:

have the meanings above given.

where n and R have the meanings above given, l0. and (2) mono-ted compound corre- 11. A method as in claim 10 wherein the by.-

where n is an integer and is at least land not h li mo r is n l ali-m l h r xide- ;more than 3, z is an integer and is at least 1 and The method p e rin 45 1120 not more than 2, R. is a member or the class consi 3114 carbamyl-m yl ulfldewhich comsisting of hydrogen and monovalent hydrocarprises electing reactions-in h P n 0! bon and halo-hydrocarbon radi l and y is a drohalide acceptor, between 4,6-diaminovz-mermember of the class consisting of oxygen and sul- 9% 8-m ne' nd l m fur, said method comprising electing reactiomin -thepresenceotaacceptor,betweenu GAETANO 1". DTALELI 3m W. UNDERWQOD. 

